A new kind of triptycene-derived calix[6]arene analogue was synthesized by two different routes. The triptycene-derived calix[6]arene analogues show highly symmetric structures and fixed conformations in solution, and can self-assemble into organic tubular structures with aromatic rings as the wall in the solid state. Moreover, the calix[6]arene analogue with two 1,8-dihydroxyltriptycene moieties in the cis position was also found to form stable complexes with paraquat derivatives with different terminal functional groups. Consequently, a [2]rotaxane assembly based on the calix[6]arene analogue was further constructed.